Catalytic Regioselective Isomerization of 2,2‐Disubstituted Oxetanes to Homoallylic Alcohols

Albert Cabré, Sergi Rafael, Giuseppe Sciortino, Gregori Ujaque, Xavier Verdaguer, Agustí Lledós, Antoni Riera

Research output: Contribution to journalArticleResearchpeer-review

Abstract

The selective isomerization of strained heterocyclic compounds is an important tool in organic synthesis. An unprecedented regioselective isomerization of 2,2-disubstituted oxetanes into homoallylic alcohols is described. The use of tris(pentafluorophenyl)borane (B(C 6F 5) 3) , a commercially available Lewis acid was key to obtaining good yields and selectivities since other Lewis acids afforded mixtures of isomers and substantial polymerization. The reaction took place under exceptionally mild reaction conditions and very low catalyst loading (0.5 mol %). DFT calculations disclose the mechanistic features of the isomerization and account for the high selectivity displayed by the B(C 6F 5) 3 catalyst. The synthetic applicability of the new reaction is demonstrated by the preparation of γ-chiral alcohols using iridium-catalyzed asymmetric hydrogenation.

Original languageAmerican English
Pages (from-to)7521-7527
Number of pages7
JournalAngewandte Chemie International Edition
Volume59
Issue number19
DOIs
Publication statusPublished - 4 May 2020

Keywords

  • allylic compounds
  • asymmetric catalysis
  • boron
  • hydrogenation
  • isomerization
  • RING EXPANSION
  • FORMAL SYNTHESIS
  • SUBSTITUTED OXETANES
  • COMPLEXES
  • DRUG DISCOVERY
  • AMINOPHOSPHINES
  • REARRANGEMENT
  • ASYMMETRIC HYDROGENATION
  • STEREOSELECTIVE-SYNTHESIS
  • DERIVATIVES

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